Regeneration of ionic liquid catalyst by hydrogenation using a metal or metal alloy catalyst

ABSTRACT

A process for regenerating a used acidic ionic liquid catalyst which has, been deactivated comprising the steps of contacting the used chloroaluminate ionic liquid catalyst and hydrogen with a metal hydrogenation catalyst in a reaction zone under hydrogenation conditions for a time sufficient to increase the activity of the ionic liquid catalyst is described. In one embodiment, hydrogenation is conducted in the presence of a hydrocarbon solvent.

FIELD OF THE INVENTION

The present invention relates to methods for the regeneration of catalysts and more specifically to the regeneration of ionic liquid catalysts.

BACKGROUND OF THE INVENTION

Ionic liquids are liquids that are composed entirely of ions. The so-called “low temperature” Ionic liquids are generally organic salts with melting points under 100 degrees C., often even lower than room temperature. Ionic liquids may be suitable for example for use as a catalyst and as a solvent in alkylation and polymerization reactions as well as in dimerization, oligomerization acetylation, metatheses, and copolymerization reactions.

One class of ionic liquids is fused salt compositions, which are molten at low temperature and are useful as catalysts, solvents and electrolytes. Such compositions are mixtures of components which are liquid at temperatures below the individual melting points of the components.

Ionic liquids can be defined as liquids whose make-up is entirely comprised of ions as a combination of cations and anions. The most common ionic liquids are those prepared from organic-based cations and inorganic or organic anions. The most common organic cations are ammonium cations, but phosphonium and sulphonium cations are also frequently used. Ionic liquids of pyridinium and imidazolium are perhaps the most commonly used cations. Anions include, but not limited to, BF₄ ⁻, PF₆ ⁻, haloaluminates such as Al₂Cl₇ ⁻ and Al₂Br₇ ⁻, [(CF₃SO₂)₂N)]⁻, alkyl sulphates (RSO₃ ⁻), carboxylates (RCO₂ ⁻) and many other. The most catalytically interesting ionic liquids are those derived from ammonium halides and Lewis acids (such as AlCl₃, TiCl₄, SnCl₄, FeCl₃ . . . etc). Chloroaluminate ionic liquids are perhaps the most commonly used ionic liquid catalyst systems.

Examples of such low temperature ionic liquids or molten fused salts are the chloroaluminate salts. Alkyl imidazolium or pyridinium salts, for example, can be mixed with aluminum trichloride (AlCl₃) to form the fused chloroaluminate salts. The use of the fused salts of 1-alkylpyridinium chloride and aluminum trichloride as electrolytes is discussed in U.S. Pat. No. 4,122,245. Other patents which discuss the use of fused salts from aluminum trichloride and alkylimidazolium halides as electrolytes are U.S. Pat. Nos. 4,463,071 and 4,463,072.

U.S. Pat. No. 5,104,840 to describes ionic liquids which comprise at least one alkylaluminum dihalide and at least one quaternary ammonium halide and/or at least one quaternary ammonium phosphonium halide; and their uses as solvents in catalytic reactions.

U.S. Pat. No. 6,096,680 describes liquid clathrate compositions useful as reusable aluminum catalysts in Friedel-Crafts reactions. In one embodiment, the liquid clathrate composition is formed from constituents comprising (i) at least one aluminum trihalide, (ii) at least one salt selected from alkali metal halide, alkaline earth metal halide, alkali metal pseudohalide, quaternary ammonium salt, quaternary phosphonium salt, or ternary sulfonium salt, or a mixture of any two or more of the foregoing, and (iii) at least one aromatic hydrocarbon compound.

Aluminum-containing catalysts are among the most common Lewis acid catalysts employed in Friedel-Craft reactions. Friedel-Craft reactions are reactions which fall within the broader category of electrophylic substitution reactions including alkylations.

Other examples of ionic liquids and their methods of preparation may also be found in U.S. Pat. Nos. 5,731,101; 6,797,853 and in U.S. Patent Application Publications 2004/0077914 and 2004/0133056.

Hydrogenation in chloroaluminate ionic liquids in the presence of an electropositive metal and HCl was reported by K. R. Seddon et al in Chem. Commun., 1999, 1043-1044.

As a result of use, ionic liquid catalysts become deactivated, i.e. lose activity, and may eventually need to be replaced. However, ionic liquid catalysts are expensive and replacement adds significantly to operating expenses by in some cases requiring shut down of an industrial process. One of the heretofore unsolved problems impeding the commercial use of chloroaluminate ionic liquid catalysts has been the inability to regenerate and recycle them. The present invention provides methods to regenerate acidic chloroaluminate ionic liquid catalysts overcoming this obstacle and paving the way for the practical, commercial use of these environmentally friendly catalysts.

SUMMARY OF THE INVENTION

Among other things, the present invention provides a process for regenerating a used acidic chloroaluminate ionic liquid catalyst comprising contacting the used chloroaluminate ionic liquid catalyst and hydrogen with a metal hydrogenation catalyst in a reaction zone under hydrogenation conditions for a time sufficient to increase the activity of the ionic liquid catalyst.

BRIEF DESCRIPTION OF THE FIGURE

The FIGURE is a block diagram of an embodiment of an ionic liquid catalyst regeneration according to the invention.

DETAILED DESCRIPTION

The present invention relates to a process for the regeneration of spent or deactivated acidic ionic liquid-based catalysts i.e. those catalysts which have lost all or some of their catalytic activity. The present process is being described and exemplified with reference certain specific ionic liquid catalysts and processes catalyzed thereby, but such description is not intended to limit the scope of the invention. The methods described may be applied to other catalysts and processes by those persons having ordinary skill based on the teachings, descriptions and examples included herein.

The specific examples used herein refer to alkylation processes using ionic liquid systems, which are amine-based cationic species mixed with aluminum chloride. In such systems, to obtain the appropriate acidity suitable for the alkylation chemistry, the ionic liquid catalyst is generally prepared to full acidity strength by mixing one molar part of the appropriate ammonium chloride with two molar parts of aluminum chloride. The catalyst exemplified for the alkylation process is a1-alkyl-pyridinium chloroaluminate, such as 1-butyl-pyridinium heptachloroaluminate.

In general, a strongly acidic ionic liquid is necessary for isoparaffin alkylation, e.g. isoparaffin alkylation. In that case, aluminum chloride, which is a strong Lewis acid in a combination with a small concentration of a Broensted acid, is a preferred catalyst component in the ionic liquid catalyst scheme.

While not being bound to this or any other theory of operation, the present invention is based in part on our discovery that one of the major catalyst deactivation mechanisms is the formation of by-products known as conjunct polymers. The term conjunct polymer was first used by Pines and Ipatieff to distinguish these polymeric molecules from the usual polymers. Unlike typical polymers, conjunct polymers are polyunsaturated cyclic, polycyclic and acyclic molecules formed by concurrent acid-catalyzed reactions including, among others, polymerization, alkylation, cyclization, and hydride transfer reactions. Conjunct polymers consist of unsaturated intricate network of molecules that may include one or a combination of 4-, 5-, 6- and 7-membered rings in their skeletons. Some examples of the likely polymeric species were reported by Miron et al. (Journal of chemical and Engineering Data, 1963) and Pines (Chem. Tech, 1982).These molecules contain double and conjugated double bonds in intricate structures containing a combination of cyclic and acyclic skeletons.

The conjunct polymers deactivate the chloroaluminate ionic liquid catalysts by weakening the acid strength of the catalyst through the formation of complexes of conjunct polymers and AlCl₃ possibly by means of electron-donor/electron-acceptor interactions. The conjunct polymers with their double bonds are the donors and the Lewis acid (AlC₃) is the acceptor. Using their double bonds, the conjunct polymers coordinate to the Lewis acid (AlCl₃) in the ionic liquid and rendering the butylpyridinium chloroaluminate catalyst less active. Thus, the acidity of the catalyst becomes weaker and the overall catalytic activity becomes compromised and no longer effective for the intended purpose. Thus, the catalyst performance will become a function of the concentration of conjunct polymers in the ionic liquid phase. As more conjunct polymers accumulate in the ionic liquid phase the catalyst becomes less active. So, removal of all or a suitable portion of the conjunct polymers from the ionic liquid phase is a significant aspect of the present process for ionic liquids catalyst regeneration.

The term “conjunct polymer” as used herein also includes any other species which might complex to AlCl₃ by pi bonding or sigma bonding or other means, which results in those species binding to the ionic liquid, so they are not removable by simple hydrocarbon extraction.

It is believed that deactivation of the catalyst by the presence of conjunct polymers is, in part at least, caused by coordination and complex formation between the Lewis acid AlCl₃ (electron pair acceptor) and the conjunct polymers (electron donors). In such complexes, the AlCl₃ is no longer available for catalysis since it is tied-up in the AlCl₃-conjunct polymers complexes. It also appears that the presence (or accumulation) of conjunct polymer molecules in the catalyst phase is not by virtue of being miscible in the ionic liquid phase. While conjunct polymers may be somewhat miscible in the ionic liquids, their accumulation in the catalyst phase is more likely to being bound by strong acid-base interactions (complexation) rather than being soluble in the ionic liquid phase.

Conjunct polymers isolated from the catalyst phase by means of hydrolysis are highly soluble in hydrocarbons. However, attempts to remove them from the catalyst phase prior to hydrolysis by simple extraction methods with hydrocarbon solvents such as hexane, decane and toluene were unsuccessful. Other more polar solvents such as CH₂Cl₂ may dissolve a chloroaluminate ionic liquid and therefore are not selective solvents for dissolving and removing conjunct polymers. Conjunct polymers may be isolated by hydrolysis. However, these methods of isolating the conjunct polymers are destructive, and result in an actual loss of a catalytic component (AlCl₃). The hydrolysis methods hydrolyze the catalytic component (AlCl₃) and transform it into inactive aluminum hydroxide and aluminum oxide. This indicates that the conjunct polymers are tightly held in the ionic liquid phase by fairly strong type of bonding system. Therefore, any successful attempt to reactivate and regenerate the catalyst must involve the removal of conjunct polymers to release aluminum trichloride from the AlCl₃-conjunct polymer complexes without destroying, consuming, or irreversibly tying up the AlCl₃. In other words, one objective is to free the catalyst by replacing the conjunct polymers with other basic species that simply displace the polymer without destroying the catalyst or by suppressing the ability of conjunct polymers to form complexes with Lewis acids (aluminum chloride).

The deactivated catalyst can be revived in a nondestructive manner by freeing up the AlCl₃ from conjunct polymer-AlCl₃ complex. In principle, this can be accomplished by saturation of the double bonds of the conjunct polymers to eliminate their ability to coordinate to the Lewis acid (AlCl₃). By hydrogenation, the double bonds of the conjunct polymers will be saturated and no longer be able to be coordinated or complexed to AlCl₃. AlCl₃ no longer bound by conjunct polymers is then released to take part in catalytic reactions.

Among other things the present invention provides a process for the removal of the conjunct polymers from a used ionic liquid catalyst by saturating the double bonds of the conjunct polymers by means of hydrogenation using a metal or metal alloy hydrogenation catalyst.

Hydrogenation is a well-established process both in the chemical and petroleum refining industries. Nickel is often used as a hydrogenation component, as are noble metals such as platinum, palladium, rhodium and iridium. Depending upon the ease with which the feed may be hydrogenated, the hydrogen pressures used may vary from quite low to very high values, typically from about 100 to 2,500 psig.

The hydrogenation catalyst used in this invention may be any one of the various metallic catalysts which have hydrogenating ability. The preferred catalyst is selected from Group VI-B and VIII. Specific examples of the metallic catalysts are Fe, Co, Ni, Ru, Rh, Pd, Ir, Os, Pt, Cr, Mn, Ti, V, Zr, Mo, and W. These metals may be used singly, in combination or as alloys. Catalysts such as Raney nickel and alloys such as Ni/Al alloy may also be suitably employed.

The metals can be in the form of fine particles, granules, sponges, gauzes, etc. Each metal may be used in any number of forms: (1) macroscopic, which includes wires, foils, fine particles, sponges, gauzes, granules, etc.; and (2) microscopic, which includes powders, smokes, colloidal suspensions, and condensed metal films.

It is known that Raney-type-metal catalysts are prepared from alloys containing one or more catalytically 25 active metals (e.g., Ni, Co, Fe, Cu, Pd, etc.) and one or more catalytically inactive, easily dissolvable metals (e.g., Al, Si, Mg, Zn). The catalytically active metal component of the alloy is present in a so-called “dissolved” state, i.e. in a finely divided form. The inactive component is removed from the alloy by leaching the same with a solvent which does not attack the active metal. As solvents, generally aqueous alkaline solutions are used. During this procedure the active metal remains in the form of finely divided catalyst. The activity of the thus-obtained catalysts is higher than that of catalysts prepared, e.g., by reducing the appropriate metal oxides. This high activity explains the importance and the widespread use of such catalysts.

As noted previously, ionic liquid catalysts may become deactivated during use. For example, in an alkylate production unit, light (C₂-C₅) olefins and isoparaffin feeds are contacted in the presence of a catalyst that promotes the alkylation reaction. In one embodiment of a process in accordance with the present invention, this catalyst is a chloroaluminate ionic liquid. The reactor, which may be a stirred tank or other type of contactor (e.g., riser reactor), produces a biphasic mixture of alkylate hydrocarbons, unreacted isoparaffins, and ionic liquid catalyst containing some conjunct polymers. The dense catalyst/conjunct polymer phase may be separated from the hydrocarbons by gravity settling in a decanter. This catalyst will be partially deactivated by the conjunct polymers binding to AlCl₃. The recovered catalyst can be reactivated in a reaction system hydrogenation with a hydrogenation catalyst. The products of this step will be reactivated catalyst and hydrogenated conjunct polymers among others as described herein. The reactivated catalyst and the hydrogenated conjunct polymers can be separated, for example, by solvent washing, decantation, and filtration.

In one embodiment of the present invention with reference to the Figure, a used ionic liquid catalyst/conjunct polymer mixture is introduced continuously into a regeneration reactor, which contains a hydrogenation catalyst.

Hydrogen gas and inert hydrocarbons in which hydrogenated conjunct polymers are soluble are fed into the reactor at the desired rate. The inert hydrocarbons may be a normal hydrocarbons ranging from C₅-C₁₅ and their mixtures, preferably C₅-C₈ although other hydrocarbons may be employed. The residence time, temperature and pressure of the reactor will be selected to allow adequate hydrogenation of the conjunct polymers. The reaction product is withdrawn and sent to a separator. This mixture is then separated into three streams, one comprising hydrogen and light hydrocarbons, a second comprising inert hydrocarbons and saturated conjunct polymers and a third comprising regenerated ionic liquid catalyst. A gravity decanter is used to separate the mixture, from which the ionic liquid phase, which is denser than other components is withdrawn. The reactivated ionic liquid catalyst is returned to the alkylation reactor. The solvent/conjunct polymer mix is separated by distillation to recover the solvent.

It is not necessary to regenerate the entire charge of catalyst. In some instances only a portion or slipstream of the catalyst charge is regenerated. In those instances only as much ionic liquid catalyst is regenerated as is necessary to maintain a desired level of catalyst activity in the process in which the ionic liquid is used as the catalyst.

The block diagram in the Figure is not meant to restrict the present invention any sort or type of reactor. Also, the Figure shows an inert hydrocarbon entering the reactor together with hydrogen and the deactivated ionic liquid. That is an optional implementation. The hydrocarbon could be left out entirely or it could be added to the separator to allow extraction and separation simultaneously. Other modifications are possible and are included in the scope of the present invention.

Hydrogenation conditions will generally include temperatures of −20° C.−200° C., preferably 50°-100° C. pressures of atmospheric-5000 psig, preferably 50-500 psig, and a contact time of 0.1 minute-24 hours, and preferably from ½-2 hours in a normal hydrocarbon as a solvent.

The following Examples are illustrative of the present invention, but are not intended to limit the invention in any way beyond what is contained in the claims which follow.

EXAMPLES Example 1 Preparation of Fresh 1-Butylpyridinium Chloroaluminate Ionic Liquid Catalyst A (Fresh IL A)

1-butyl-pyridinium chloroaluminate is a room temperature ionic liquid prepared by mixing neat 1-butyl-pyridinium chloride (a solid) with neat solid aluminum trichloride in an inert atmosphere. The syntheses of butylpyridinium chloride and the corresponding 1-butyl-pyridinium chloroaluminate are described below. In a 2-L Teflon-lined autoclave, 400 gm (5.05 mol.) anhydrous pyridine (99.9% pure purchased from Aldrich) were mixed with 650 gm (7 mol.) 1-chlorobutane (99.5% pure purchased from Aldrich). The neat mixture was sealed and let to stir at 125° C. under autogenic pressure over night. After cooling off the autoclave and venting it, the reaction mix was diluted and dissolved in chloroform and transferred to a three liter round bottom flask. Concentration of the reaction mixture at reduced pressure on a rotary evaporator (in a hot water bath) to remove excess chloride, un-reacted pyridine and the chloroform solvent gave a tan solid product. Purification of the product was done by dissolving the obtained solids in hot acetone and precipitating the pure product through cooling and addition of diethyl ether. Filtering and drying under vacuum and heat on a rotary evaporator gave 750 gm (88% yields) of the desired product as an off-white shiny solid. ¹H-NMR and ¹³C-NMR were consistent with the desired 1-butyl-pyridinium chloride and no impurities were observed.

1-butylpyridinium chloroaluminate was prepared by slowly mixing dried 1-butylpyridinium chloride and anhydrous aluminum chloride (AlCl₃) according to the following procedure. The 1-butylpyridinium chloride (prepared as described above) was dried under vacuum at 80° C. for 48 hours to get rid of residual water (1-butylpyridinium chloride is hydroscopic and readily absorbs water from exposure to air). Five hundred grams (2.91 mol.) of the dried 1-butylpyridinium chloride were transferred to a 2-Liter beaker in a nitrogen atmosphere in a glove box. Then, 777.4 gm (5.83 mol.) of anhydrous powdered AlCl₃ (99.99% from Aldrich) were added in small portions (while stirring) to control the temperature of the highly exothermic reaction. Once all the AlCl₃ was added, the resulting amber-looking liquid was left to gently stir overnight in the glove box. The liquid was then filtered to remove any un-dissolved AlCl₃. The resulting acidic 1-butyl-pyridinium chloroaluminate was used as the catalyst for the alkylation of isopentane with ethylene.

Example 2 Preparation of “Deactivated” 1-Butylpyridinium Chloroaluminate Ionic Liquid Catalyst (Deactivated Catalyst A)

“Deactivated” or “used” 1-butylpyridinium chloroaluminate ionic liquid catalyst was prepared from “fresh” 1-butylpyridinium chloroaluminate ionic liquid catalyst by carrying out the isobutane alkylation reaction in a continuous flow microunit under catalyst recycle with accelerated fouling conditions.

The microunit consists of feed pumps for isobutane and butenes, a stirred autoclave reactor, a back pressure regulator, a three phase separator, and a third pump to recycle the separated ionic liquid catalyst back to the reactor. The reactor was operated at 80 to 100 psig pressure and with cooling to maintain a reaction temperature of ˜10° C. To start the reaction, isobutane, butenes, and HCl were pumped into the autoclave at the desired molar ratio (isobutane/butenes>1.0), through the back pressure regulator, and into the three phase separator. At the same time, fresh chloroaluminate ionic liquid catalyst was pumped into the reactor at a rate pre-calculated to give the desired catalyst/feed ratio on a volumetric basis. As the reaction proceeded, ionic liquid separated from the reactor effluent and collected in the bottom of the three phase separator. When a sufficient level of catalyst built up in the bottom of the separator, the flow of fresh ionic liquid was stopped and catalyst recycle from the bottom of the separator was started. In this way, the initial catalyst charge was continually used and recycled in the process.

The following process conditions were used to generate Deactivated Catalyst A (1-butylpyridinium chloroaluminate ionic liquid catalyst) from Fresh Catalyst A:

Process Variable Isobutane pump rate 4.6 g/min Butene pump rate 2.2 g/min IL Catalyst pump rate 1.6 g/min HCl flow rate 3.0 SCCM pressure 100 psig temperature 10 ° C.

The reaction was continued for 72 hours when it was judged that the catalyst had become sufficiently deactivated.

Example 3 Determination of the Amounts of Conjunct Polymer and Olefin Oligomers in Deactivated IL A

The wt % of conjunct polymers in the spent (deactivated) ionic liquid was determined by hydrolysis of known weights of the spent catalyst. The example below is a typical procedure for measuring conjunct polymers in a given spent catalyst. In a glove box, 15 gm of a spent ionic liquid catalyst in a flask were rinsed first with 30-50 ml of anhydrous hexane to remove (from the spent catalyst) any residual hydrocarbon or olefinic oligomers. The hexane rinse was concentrated under reduced pressure to give only 0.02 gm of yellow oil (0.13%). Then, 50 ml of anhydrous hexane was added to the rinsed catalyst followed by slow addition of 15 ml of water, and the mixture was stirred at 0° C. for 15-20 minutes. The resulting mixture was diluted with additional 30 ml hexanes and stirred well for additional 5-10 minutes. The mixture was allowed to settle down to two layers solution and some solid residue. The organic layer was recovered by decanting. The aqueous layer was further washed with additional 50 ml hexanes. The hexanes layers were combined and dried over anhydrous MgSO₄, filtered and concentrated to give 2.5 gm (16.7 wt % of the spent catalyst) of viscous dark orange-reddish oil. It was determined therefore that this particular spent catalyst contains 0.13% oligomers and 16.7% conjunct polymers. The hydrolysis can also be accomplished using acidic (aqueous HCl) or basic (aqueous NaOH) solutions.

Example 4 Characterization of Recovered Conjunct Polymer from Deactivated IL A

The recovered conjunct polymers according to the procedure described in Example 3 were characterized by elemental analysis and by infrared, NMR, GC-Mass and UV and spectroscopy methods. The recovered conjunct polymers have hydrogen/carbon ratio of 1.76 and chlorine content of 0.8%. ¹H-NMR and ¹³C-NMR showed the presence of olefinic protons and olefinic carbons. Infra Red indicated the presence of olefinic regions and the presence of cyclic systems and substituted double bonds. GCMS showed the conjunct polymers to have molecular weights ranging from 150-mid 600s. The recovered conjunct polymers have boiling ranges of 350-1100° F. as indicated by high boiling simulated distillation analysis. UV spectroscopy showed a UV λ_(max) at 250 nm pointing highly conjugated double bonds systems.

Example 5 Removal of Conjunct Polymer from Deactivated Catalyst A by Hydrogenation over Ni—Al Alloy

As a way for regenerating deactivated chloroaluminate ionic liquids, 35 gm of spent ionic liquids containing 22.3 wt % (7.8 gm) conjunct polymers in a 300 cc autoclave, 2 gm of Ni—Al alloy and 70 ml of anhydrous hexane were added. The autoclave was sealed and pressurized with hydrogen to 500 psi and heated to 100° C. while stirring at >1200 rpm for ˜1.5 hrs. The starting pressure was 500 psig at room temperature. As the autoclave heated up, the pressure rose to 620 psig. As the reaction continued, pressure dropped to 560 psig and remained at that pressure for the remainder of the reaction time. The reactor was cooled down and to the contents allowed to settle. The resultant reaction mixture contained the hexane layer (the top layer), the ionic liquid layer (the bottom layer) and the Ni—Al alloy settled to the bottom of the reactor. The hexane layer was decanted off and saved. The ionic liquid layer was rinsed 3×50 ml anhydrous hexane. The hexane from the reaction and all hexane rinses were combined and dried over MgSO4. Filtration and concentration of the hexane under reduced pressure (˜24 torr) in a hot water bath (˜75° C.) gave 6.9 gm of slightly faint yellow oil (88.5% of the expected saturated conjunct polymers). The total conjunct polymers removed by hydrogenation over Ni—Al at 100° C. and 500 psi H₂ pressure was 94%.

Example 6

Example 5 above was repeated with 50 gm of spent ionic liquid containing 24.3 wt % (12.15 gm) conjunct polymers in 70 cc hexane in the presence of 3 gm of Ni—Al alloy at 100° C. and starting hydrogen pressure of 500 psi. The reaction ran for 1.5 hrs. A total of 11.5 gm (94.6%) conjunct polymers were removed from the spent catalyst based on obtained saturated polymers and recovered CPs from the hydrolysis of 10 gm portion of the treated ionic liquid catalyst. The remainder of the treated ionic liquid catalyst was saved and tested for activity as described in example 12.

Example 7 Washing and Reusing Once Used Ni—Al Alloy Catalyst for Hydrogenation of Conjunct Polymers in Spent Chloroaluminate Ionic Liquid Catalyst

The Ni—Al alloy catalyst that was used to hydrogenate conjunct polymers in the spent catalyst as described in Example 5 above was recovered by filtration. This recovered catalyst was rinsed with anhydrous methylene chloride (CH₂Cl₂) in frit glass funnel under house vacuum in glove box. The rinsed Ni—Al catalyst was dried under house vacuum and used again as in Example 5. The results showed the same degree of removal of conjunct polymers as in Example 5.

Example 8 Hydrogenation of Conjunct Polymers in Spent Chloroaluminate Ionic Liquid Catalyst over Nickel Metal

As in Example 5 above, 25 gm of spent chloroaluminate ionic liquid catalyst containing 15.5 wt % (3.87 gm) conjunct polymers in 60 ml anhydrous hexane (in 300 cc autoclave) was hydrogenated at 100° C. and 500 psi hydrogen pressure over Nickel metal (3 gm) for 1.5 hours. Once the heating started, the pressure steadily started rising until it reached 946 psi at 100° C. The pressure dropped slightly to 910 psi at the end of the run. The reaction was stopped and the organic phase containing the hydrogenated polymers was decanted off. The ionic liquid-Ni residue was rinsed with 2×50 ml anhydrous hexane. All the organic layers were combined and dried over MgSO4. Filtration and concentration to remove hexane gave 1.58 gm (41%) of the hydrogenated polymers as colorless oil. The ionic liquid catalyst was separated from Nickel metal by filtration. The ionic liquid catalyst was entirely hydrolyzed giving 1.62 gm conjunct polymers (the total amount of CPs remaining in the catalyst). This indicates that hydrogenation over Nickel metal led to the overall removal of 2.2 gm (58%) of the conjunct polymers from the spent catalyst.

Example 9 Removal of Conjunct Polymer from Deactivated Catalyst by Hydrogenation with Nickel Boride Catalyst

The procedure of Example 5 was repeated using 22.00 gram of spent chloroaluminate ionic liquid containing 7.75 wt % conjunct polymer. The hydrogenation catalyst was 1.0 gram of nickel boride catalyst. In this experiment, no hexane was added to aid stirring. The initial pressure at 100° C. was ˜1312 psig and after heating 4.5 hours at 100° C., the pressure was ˜1300 psig. After extraction of hexane and evaporation of light components, no oil was recovered.

The entire sample of the deactivated Chloroaluminate ionic liquid after hydrogenation and hexane extraction was placed in a bottle and hydrolyzed as described in Example 3. After hexane extraction and evaporation of the volatiles from the combined hexane extracts, a residue of 0.97 g of conjunct polymer was obtained. This corresponds to a conjunct polymer content after hydrogenation of 4.41 wt %. Alternatively, 43.1 wt % of the conjunct polymer originally present in Deactivated Catalyst A was removed by hydrogenation.

Example 10 Determination of the Activity of the Regenerated ButylPyridinium Chloroaluminate Ionic Liquid Catalyst by Hydrogenation over Ni—Al Alloy

The regenerated butylpyridinium chloroaluminate ionic liquid catalyst described in Examples 5 and 6 was tested for activity by using it as the catalyst in the alkylation of isopentane with ethylene and comparing it with freshly-made catalyst. The alkylation of isopentane with ethylene was done according to the following procedure A 300 cc autoclave was charged with 20 gm of ionic liquid catalyst, 100 gm anhydrous isopentane, 10 gm ethylene and 0.3 gm anhydrous HCl. The reaction was then stirred ˜1200 rpm and heated to 50° C. at autogenic pressures. The starting pressure was usually 280-320 psi. The reaction was usually complete when the pressure dropped down to single digits. In the case of slow going reaction, the reaction was allowed to go on for 1 hr. At the end of the reaction, the reactor was vented out and a gas sample was checked by GC for ethylene concentration. The liquid reaction mixture was allowed to settle into 2 phases. The organic phase was decanted and analyzed for product distribution by GC analysis. The following Table 1 draws a comparison among the freshly made, the spent and the regenerated catalysts.

TABLE 1 Fresh Ionic Spent Ionic Ni—Al Regen. Liquid Catalyst Liquid Catalyst Ionic Liquid Cat. Reaction Time 6-9 min. 60 min. 4-7 min. Starting 300 psi 286 psi 350 psi Pressure Ending pressure 11 302 psi 7 iC5 wt % 72 98 61 C7s wt %: 2,3-DM-Pentane 8.23 0.9 8.5 2,4-DM-Pentane 10 0.6 11.3 Other C7s 0.77 0.1 1.2 2,3DM/2,4DM 0.82 1.5 0.75 

1. A process for regenerating a used acidic ionic liquid catalyst, comprising contacting the used acidic ionic liquid catalyst and hydrogen with a metal hydrogenation catalyst in a reaction zone under hydrogenation conditions for a time sufficient to increase the activity of the used acidic ionic liquid catalyst for isoparaffin alkylation.
 2. The process according to claim 1, wherein the hydrogenation catalyst is selected from the group consisting of Group VI-B and VIII elements, their alloys and their mixtures.
 3. The process according to claim 1, wherein the metal hydrogenation catalyst is a Raney metal catalyst.
 4. The process according to claim 1, wherein the metal hydrogenation catalyst is in a microscopic form.
 5. The process according to claim 1, wherein the metal hydrogenation catalyst is in a macroscopic form.
 6. The process according to claim 1, wherein the reaction zone contains an inert hydrocarbon in which saturated conjunct polymers are soluble.
 7. The process according to claim 6, wherein the inert hydrocarbon is selected from the group consisting of normal hydrocarbons ranging from C₅-C₁₅ and their mixtures.
 8. The process-according to claim 1, wherein the used acidic ionic liquid catalyst has been used to catalyze a Friedel-Craft reaction.
 9. The process according to claim 8, wherein the Friedel-Craft reaction is alkylation.
 10. The-process according to claim 1, wherein the used acidic ionic liquid catalyst comprises an imidazolium, a pyridinium, a phosphonium, a tetralkylammonium derivative, or their mixtures.
 11. The process according to claim 1, wherein the used acidic ionic liquid catalyst is a chloroaluminate ionic liquid.
 12. The process according to claim 11, wherein the chloroaluminate ionic liquid is a 1-alkyl-pyridinium chloroaluminate.
 13. A process for regenerating a used acidic ionic liquid catalyst which has been deactivated by a conjunct polymers, comprising contacting the used acidic ionic liquid catalyst which has been deactivated by the conjunct polymer and hydrogen with a metal hydrogenation catalyst in a reaction zone under hydrogenation conditions, in the presence of an inert-hydrocarbon in which saturated conjunct polymers are soluble, for a time sufficient to hydrogenate at least a portion of the conjunct polymers and to increase the activity of the used acidic ionic liquid catalyst for isoparaffin alkylation.
 14. The process according to claim 13, wherein the inert hydrocarbon is selected from the group consisting of normal hydrocarbons ranging from C₅-C₁₅ and their mixtures.
 15. The process-according to claim 13, wherein the metal hydrogenation catalyst is selected from the group consisting of Group VI-B and VIII elements, their alloys and their mixtures.
 16. The process according to claim 13, wherein the metal hydrogenation catalyst is a Raney metal catalyst.
 17. The process according to claim 13, wherein the metal hydrogenation catalyst is in a microscopic form.
 18. The process according to claim 13, wherein the metal hydrogenation catalyst is in a macroscopic form.
 19. The process according to claim 13, wherein the used acidic ionic liquid catalyst has been used to catalyze a Friedel-Craft reaction.
 20. The process according to claim 19, wherein the Friedel-Craft reaction is alkylation.
 21. The process according to claim 13, wherein the used acidic ionic liquid catalyst comprises an imidazolium, a pyridinium, a phosphonium, a tetralkylammonium derivative, or their mixtures.
 22. The process according to claim 13, wherein the used acidic ionic liquid catalyst is a chloroaluminate ionic liquid.
 23. The process according to claim 21, wherein the used acidic ionic liquid catalyst is a chloroaluminate ionic liquid. 